A Combined Computational–Experimental Study of the Kinetics of Intramolecular Diels–AlderReactions in a Series of 1,3,8-Nonatrienes
MetadataShow full item record
Activation enthalpies for a series of five 1,3,8-nonatriene intramolecular Diels–Alder (IMDA) reactions involving substrates 1–5 have been determined experimentally and Singleton’s natural abundance method has been employed to determine kinetic isotope effects in the IMDA reaction of fumarate 3. The activation enthalpies for the IMDA reactions of the systems possessing a –CH2OCH2– diene/dienophile tether are significantly smaller than their counterparts possessingthe –CH2OC(¼O)– tether. The experimental activation enthalpies have been used to benchmark computed values from four model chemistries, namely two density functional theory functionals, B3LYP and M06-2X, and two generally very accurate composite ab initio wave function methods, CBS-QB3 and G4(MP2). G4(MP2) outperformed the computationally more expensive CBS-QB3 method, but the vastly cheaper M06-2X/6-31G(d)//B3LYP/6-31G(d) method was sufficiently accurate to be the recommended method of choice for calculating activation parameters. Experimental 2H kinetic isotope effects for the IMDA reaction of fumarate 3 confirmed the computational predictions that this Diels–Alder reaction is concerted but asynchronous.
Showing items related by title, author, creator and subject.
Aragonès, A.; Haworth, N.; Darwish, Nadim; Ciampi, S.; Bloomfield, N.; Wallace, G.; Diez-Perez, I.; Coote, M. (2016)It is often thought that the ability to control reaction rates with an applied electrical potential gradient is unique to redox systems. However, recent theoretical studies suggest that oriented electric fields could ...
Catalytic partial oxidation of propylene to acrolein: the catalyst structure, reaction mechanisms and kineticsFansuri, Hamzah (2005)Bismuth molybdates have long been known as active catalysts for selective oxidation of olefins. There are several phases of bismuth molybdates but only three of them are known to be active for partial oxidation of propylene ...
Hidalgo, T.; Kuhar, L.; Beinlich, Andreas; Putnis, Andrew (2018)© 2018 The suitability of methanesulfonic acid as a copper lixiviant with ferric chloride as an oxidant was studied by analysing the leaching kinetics and by characterising solid residues from leach tests on a chalcopyrite-rich ...